Process for copolymerizing alpha-monoolefins with or without a polyene,using catalyst comprising organoaluminum compound and vanadyl compound containing cyclic hydrocarbon group

ABSTRACT

Ethylene, propylene and similar olefins, with or without a conjugated or non-conjugated polyene (e.g., isoprene, 1,4hexadiene, 5-ethylidene-2-norbornene) are copolymerized in solution with a catalyst based on organoaluminum compound (e.g., ethylaluminum sesquichloride) and vanadyl compound of the type VO(ORm)X3 m where R is cyclic hydrocarbon, X is halogen and m is 1 to 3 (e.g., vanadyl tricyclohexoide, monovanadyl dicyclohexoxide, dichlorovanadyl bornyloxide, monochlorovanadyl dinorbornyloxide). Use of a vanadyl compound having a cyclic hydrocarbon substituent provides a catalyst having enhanced ability to incorporate diene, including conjugated diene, into the copolymer.

United States Patent Yamamoto et al.

154! PROCESS FOR COPOLYMERIZING ALPHA-MONOOLEFINS WITH OR WITHOUT APOLYENE, USING CATALYST COMPRISING ORGANOALUMINUM COMPOUND AND VANADYLCOMPOUND CONTAINING CYCLIC I-IYDROCARBON GROUP [72] Inventors: KeisakuYamamoto, lbarakk Hiroyoshi Takao, Takatsuki; Masaaki Hirooka, lbaraki;Teruo Oshima, Nishinomiya,

allofJapan [73] Assignee: Sumitomo Chemical Company Limited,"

Osaka, Japan [22] Filed: July 23,1969

21 Appl. No.: 844,187

[30] Foreign Application Priority Data July 30, 1968 Japan ..43/538l5[52] US. Cl. ..260/80.78, 260/882 R [51] Int. Cl. ..C08f 15/40, C08f19/00, C08f 15/04 [58] Field of Search ..260/88.2 R, 80.78

[ 1 July4, 1972 [56] References Cited UNITED STATES PATENTS Matthews etal ..260/80:78

Primary Examiner.loseph L. Schofer Assistant ExaminerRichard A. GaitherAtt0meyJames J. Long 57 ABSTRACT 28 Claims, N0 Drawings PROCESS FORCOPOLYMERIZING ALPHA- MONOOLEFINS WITH OR WITHOUT A POLYENE, USINGCATALYST COMPRISING ORGANOALUMINUM COMPOUND AND VANADYL COMPOUNDCONTAINING CYCLIC HYDROCARBON GROUP Our copending application Ser. No.844,178 filed of even date herewith claims, as new chemicals andcompositions, the vanadium compounds and catalysts employed in thepolymerization process of this invention.

The present invention relates to a process for producing an olefinichydrocarbon copolymer by the use of a novel catalyst which comprises asessential components a novel vanadium compound and an organic aluminumcompound. In more particular, the present invention relates to a processfor producing an amorphous olefinic hydrocarbon copolymer in which apolyene compound is effectively introduced by the aid of a 1 novelcatalyst.

There have heretofore been proposed various processes for producing anamorphous olefin copolymer. Particularly, Ziegler Natta type catalystsare effective and among them, the combinations of a vanadium compoundwith an organic aluminum compound are excellent. Representative kinds ofsaid vanadium compounds include a halogen compounds, alkoxy compounds,acetyl acetonates and the like. These have industrial merit for thepurpose of producing an amorphous copolymer.

In producing suIfur-vulcanizable rubbery compounds by copolymerizingethylene, a-olefins and diene compounds or other polyene compounds, withthe use of the Ziegler-Natta type catalysts, the diene compounds orother polyene compounds, particularly conjugated diene compounds, havein general a retarding effect on the polymerization. Italian Pat. No.664,769 (British Pat. No. 983,437) proposes a process for readilycopolymerizing a conjugated diolefin with the use of an organoaluminumcompound containing a bulky substituent.

In general, the Ziegler-Natta type catalysts which use vanadiumcompounds containing alkoxy groups such as vanadyl trialkoxide VO(OR)mono-halogenated vanadyl alkoxide VO( OR X and di-halogenated vanadylmonoalkoxide VO(OR)X are suitable for the production of a copolymerhaving narrow molecular weight distribution and compositiondistribution, and produce a high yield of copolymers per a unit weightof the catalysts.

The use of such a compound containing an alkoxy group as a catalyst inthe polymerization and copolymerization of olefins has been proposed inJapanese Pat. Publication No. 7394/1961, Japanese Pat. Publication No.7132/ I963, Japanese Pat. Publication No. 13790/1963 and the like. Thehydrocarbon residue in the disclosed alkoxy groups is a straight-chainor branched-chain aliphatic group. The active site of the Ziegler-Nattatype catalysts in the polymerization has been reported to exist on thetransition metal. However, the effect of a stereometrically bulky groupattached to a transition metal has not been known. The present inventorshave found that when a stereometrically bulky group containing a cyclichydrocarbon group having five or more carbon atoms, particularly acycloaliphatic hydrocarbon group, including, bridged cyclic hydrocarbongroup, spiro type hydrocarbon group and the like, is introduced as theaforedescribed hydrocarbon residue of the alkoxy compound of vanadiumand the resulting novel vanadium compound is employed as thevanadium-containing component of the catalyst, such catalyst hasexcellent polymerization activity and readily makes a polyene compound,especially a diene compound, copolymen'ze. Further, this kind of novelpolymerization catalyst can be used for the copolymerization ofethylene, propylene or other a-olefins in general.

That is to say, the present invention provides a process of producing anolefinic hydrocarbon copolymer, characterized by contacting ethylene, ana-olefin having 3 to 20 carbon atoms and, if desired, a polyenecompound, with (A) a vanadium compound having the general formulaVO(OR),,,X wherein R is a group containing a cyclic hydrocarbon having 5to 20 carbon atoms, X is a halogen atom, and m is an integer from 1 to3, and (B) an organoaluminum compound having the general formulaAlR,,X':, wherein R is a hydrocarbon group having 1 to 20 carbon atoms,X is a halogen or hydrogen atom, and n is a number from I to 3.

The cyclic hydrocarbon radical represented by R in the general formulafor the vanadium compound (A) can include, for example, an alicyclichydrocarbon group, bridged cyclic hydrocarbon group, spiro typehydrocarbon group and the like. These groups are exemplified bycyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-cyclopentenyl,2-cyclohexenyl, 2- cycloheptenyl, 4-cyclooctenyl, 2-methy-cyclopentyl,3-tertiary-butyl-cyclohexyl, 4-phenyl-cyclohexyl,1,3-dimethylcyclohexyl, 3-methyl-6-isopropyl-cyclohexyl,cyclopentylmethyl, cyclohexyl-ethyl, cycloheptyl-ethyl,2,2-biscyclohexyl-ethyl, 2-norbomyl, bornyl, 5-norbomen-2-yl, 3-pinanyl,cyclopentane-spiro-cyclobutan-3-yl, spiro-bicyclohexan-4- yl, Z-indenyl,l -indanyl and the like.

Compounds having such groups are illustrated by vanadyltricyclopentoxide, vanadyl tricyclohexoxide, vanadyl tri-(3-cyclopentenoxide), vanadyl tri-(3-methyl-cyclohexoxide), vanadyl tri-(3-tertiary-butylcyclohexoxidc), vanadyl trimenthoxide, vanadyltri-(cyclohexylmenthoxide), vanadyl tribomyloxide, vanadyltri-(S-norbomen-Z-yloxide), vanadyl tri-( Z-indanyloxidechlorovanadyl-di-( cyclopentoxid e chlorovanadyl-di-(cyclohexoxide),chlorovanadyl-di-( 3- cyclopentenoxide),chlorovanadyl-di-(3-methyl-cyclohexoxide), chlorovanadyl-di-(3-tertiary-butyl-cyclohexoxide chlorovanadyl-di-(menthoxide),chlorovanadyl-di-(cyclohex ylmethoxide), chlorovanadyl-di-( bomyloxidechlorovanadyldi-( 5-norbomene-2-yloxidechlorovanadyldi-(Z-indanyloxide), dichlorovanadyl-cyclopentoxide.dichlorovanadyl-cyclohexoxide, dichl0rovanadyl-( 3- cyclopentenoxide),dichlorovanadyl-(3-methyl-cyclohexoxide), dichlorovanadyl-(3-tertiary-butyl-cyclohexoxide dichlorovanadyl-menthoxide,dichlorovanadyl-(cyclohexylmethoxide), dichlorovanadyl-bomyloxide,dichlorovanadyl- (5 -norbornene-2-yloxide dichlorovanadyl-(Z-indanyloxide) and the like.

These vanadium compounds may be synthesized, for example, in accordancewith the following processes:

a. A vanadium compound having the general formula VO(OR),,,X3 m whereinR is an alkyl group having one to five carbon atoms, X is a halogenatom, and m is an integer of l to 3, is contacted with an alcohol havingthe general formula ROH wherein R is a group containing a cyclichydrocarbon having 5 to 20 carbon atoms.

b. Vanadyl trichloride is contacted with an alcohol having the generalformula ROI-I wherein R has the same significance as mentioned above.

c. A vanadium compound having the general formula VO(OR);, wherein R hasthe same significance as mentioned above is contacted with a carboxylichalide having the general formula R"COCl wherein R has the samesignificance as mentioned above.

The vanadyl trialkoxide compounds referred to in the present process maybe synthesized, for example, by ester interchange reaction between analcohol (ROI-I) having said group containing the cyclic hydrocarbon andvanadyl ethoxide in an inert solvent, and thereafter removing anazeotrope of ethanol and solvent. The reaction proceeds as follows:

Further, the vanadyl halogen alkoxides may be synthesized, for example,by reacting a vanadyl trialkoxide having said group containing thecyclic hydrocarbon with acetyl chloride in an inert solvent, and thenremoving the solvent and acetic ester. The reaction proceeds as follows:

Furthermore, a vanadyl trialkoxide compound or a vanadyl halogenalkoxide may be produced by reacting vanadyl trichloride with an alcoholhaving the group containing the cyclic hydrocarbon in an inert solvent.

The reaction proceeds as follows:

In the case where two or more of the groups containing the cyclichydrocarbon exist in the vanadium compounds thus reproduced, said groupsmay of course be identical with or different from one another.

Further, these vanadium compounds are not required to be singlecompounds, and mixtures of two kinds or more of said compounds and insome cases, reaction mixtures produced by the foregoing variousreactions may also be used as they are as one component of thepolymerization catalysts.

These reactions may be carried out in the absence of a solvent, but aremore efficaciously carried out in an inert solvent. As a solvent ahydrocarbon compound or a halogenated hydrocarbon compound is preferred.For example, there may be mentioned hexane, heptane, octane, petroleumether, ligroin, other petroleum fractions, benzene, toluene, xylene,cyclohexane, methyl cyclohexane, methylene dichloride, ethylenedichloride, chlorobenzene and the like.

In particular, the use of an aromatic hydrocarbon compound such asbenzene and the like is preferred because it forms an azeotrope with thealcohol or ester, and the reaction proceeds unifonnly. The use of analiphatic hydrocarbon such as heptane causes tar-like materials to beformed as byproducts in some cases. However, the use of the aromaticcompounds usually gives a uniform system.

The organoaluminum compounds used in the present process are representedby the general formula AlR',,X' In said general formula, R is a groupsuch as an alkyl, aryl, aralkyl, alkylaryl, cycloalkyl and the like, andis particularly preferred to be an alkyl group having one to eightcarbon atoms. Further, said R may be other hydrocarbon groups, forexample, a group such as alkenyl, cyclopentadienyl and the like,ifdesired.

X is chlorine, bromine or iodine, and may be fluorine, if desired, and nis a positive number of 3 or less, preferably 1, 1.5, 2 or 3. Thesecompounds are exemplified by methyl aluminum dichloride, ethyl aluminumdichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide,allyl aluminum dichloride, vinyl aluminum dichloride, ethyl aluminumsesquichloride, methyl aluminum sesquichloride, methyl aluminumsesquibromide, ethyl aluminum sesquiiodide, isobutyl aluminumsesquichloride, hexyl aluminum sesquichloride, diethyl aluminumchloride, diethyl aluminum bromide, dipropyl aluminum chloride,didodecyl aluminum chloride, diethyl aluminum fluoride, ethylphenylaluminum chloride, trimethyl aluminum, triethyl aluminum, tripropylaluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum,aluminum hydrides, mixtures of these compounds, mixtures thereof with ahalogenated aluminum such as aluminum chloride, aluminum bromide andaluminum iodide, and the like. Among these organic aluminum compounds,an alkylaluminium halogen compound specifically gives the preferredresult.

The present process is a process for carrying out the polymerizationwith the use of a catalyst system having the afore-described vanadiumcompounds and organic aluminum compounds as essential components.However, if required, other appropriate compounds may be added theretoas a third component. As said compounds, there can be enumerated, forexample, a compound which is an electron donor and forms a coordinationcompound or a charge transfer complex with the organic aluminumcompounds or vanadium compounds, e.g. amines, cycle-nitrogen compounds,acid amides, ethers, esters, ketones, aldehydes, a compound of elementsin the Vb Group such as phosphorus, arsenic, antimony, bismuth and thelike, various chelating agents, or the like. Or, there are availablevarious oxidizing compounds which are considered effective forpreventing excessive reduction of vanadium compounds by the organicaluminum compounds. Among these, there may be mentioned halogens,sulfur, metal halides, oxygen, nitro compounds, nitroso compounds,organic nitrates, nitrites, N-oxide compounds, p-oxide compounds, azocompounds, organic sulfides. disulfides, quinones, acid halides and thelike. Or, a reagent having molecular weight regulating effect, forexample, hydrogen or the like can be further added.

The a-olefins used in the present process are represented by the generalformula CH =CH'R" wherein R is a hydrocarbon group having 1 to 20 carbonatoms. There may be mentioned as representatives thereof propylene,butene-l, pentene-l, 3-methyl-butene-l, hexene-l, 3-methylpentene-l, 4-methyl-pentene-l, heptene-l, decene-l, vinyl-cyclopentane and the like.Among these, a lower alkene such as propylene, butene-l and the like isspecifically often used.

A sulfur-vulcanizable elastomer can be produced by adding a polyenecompound in the production of an amorphous copolymer of ethylene anda-olefins. As this kind of polyene compound, there can be usedconjugated diene compounds such as isoprene, piperylene and the like andnon-conjugated polyene compounds such as bridged cyclic hydrocarboncompounds, monocyclic compounds, heterocyclic compounds, acycliccompounds, spiro type compounds and the like. As the non-conjugatedpolyene compounds, there may be mentioned as examples dicyclopentadiene,tricyclopentadiene, S-methyl- 2,5-norbornadiene,S-methylene-Z-norbornene, S-ethylidene- 2-norbomene,5isopropylidene-Z-norbornene, 5-isopropenyl- 2-norbomene,5-(l'-butenyl)-2-norbornene, 5-(2'-butenyl)- 2-norbornene,cyclooctadiene, vinylcyclohexene, 1,5,9- cyclododecatolyene,6-methyl-4,7,8,9-tetrahydroindene, 2,2- dicyclopentenyl, transl,2-divinylcyclobutane, 1,4-hexadiene, 1,6-octadiene,6-methyl-l,5-heptadiene and the like. Even aliphatic diene compoundswhich have heretofore been known not to copolymerize readily can becopolymerized readily.

There is specifically no restriction in the ratio between the organicaluminum compounds and the vanadium compounds used in the presentprocess, but the use of a molar ratio of 1:1 to 10,000:] and the like,particularly 2:1 to 300:1, brings about the preferred result readily.Regarding the concentration in the reaction medium, a concentration ofvanadium compounds of 0.01 to 50 millimoles/l., particularly 0.1 to 10millimoles/l., is often used. However, in some cases, even a lowerconcentration of 0.01 millimole/l. or less, for example the order of 10millimole/L, shows excellent activity. As the concentration of organicaluminum compounds in the reaction system, a concentration of 0.1 to 100millimoles/l. particularly l to 20 millimolesll, is often used.

There is specifically no restriction in the sequence of addition of thecatalysts and monomers, and the addition thereof may be carried out inaccordance with conventional procedure. However, in general, theprocedure of adding separately the catalyst components (A) and (B) tothe polymerization system in the presence of monomers gives highercatalytic activity than does the use of a pre-mixture of said catalystcomponents. However, in view of the change in the catalytic activitywith elapsed time, there are some cases where it is better to use aproduct obtained by mixing and reacting the catalyst components inadvance.

The monomer components, particularly the polyene compounds, may bedissolved in advance in the reaction medium or may be added continuouslyor intermittently.

In the production of amorphous elastomers in the present process, such acharging condition is preferred that the ethylene constitutes molepercent or less of the mixture of ethylene and alpha-olefins.

The polymerization reaction can be carried out under a reduced pressureor under an elevated pressure up to Kg./cm". Inert gases may be present.As the polymerization temperature, any conventional temperature from alow temperature such as 78 C. to a heated state such as +l00 C.

5588 Illll-H llu'v can be used, but in general, a temperature in therange of 35 C. to 70 C. gives favorable results. The catalysts in thepresent process are excellent in the durability of catalytic activity,but it is desirable to polymerize at a relatively low temperature toprolong the catalytic activity and achieve high catalytic efiiciency.

In the operation of the present process, the polymerization may becarried out in the absence of a solvent, for example, in a liquefiedmonomer, or with the use of an inert medium. As the inert medium, ahydrocarbon compound or a halogenated hydrocarbon compound is suitable.For example, there can be mentioned propane, butane, pentane, hexane,heptane, octane, petroleum ether, ligroin, other petroleum mixedsolvents, benzene, toluene, xylene, cyclohexane, methyl cyclohexane,methylene dichloride, ethylene dichloride, trichloroethane,tetrachloroethane, butyl chloride, chlorobenzene, bromobenzene and thelike.

After completion of the polymerization reaction, the resultant polymercan be purified and recovered by aftertreatment in the usual manner.Applicable treatments are alcohol treatment, alcohol-hydrochloric acidtreatment, water treatment, steam treatment, aqueous hydrochloric acidtreatment, alkali treatment, aqueous emulsifier solution treatment,after-treatment with chelating agents and other conventionalafter-treatments useful for polymerizates obtained with theZiegler-Natta catalysts. Alternatively, the solid material may berecovered by salting out without said treatments or by removing thesolvent as it is. A stabilizer or other additives may be added during orafter said treatments.

The present process will be further substantially explained withreference to the following examples, but the present process is not tobe limited by these examples.

EXAMPLE 1 A 150 ml. four-necked flask provided with a stirrer,thermometer, dropping funnel and reflux condenser was evacuated andfilled with argon. Then 20.1 g. (100 millimoles) of vanadyl triethoxidedissolved in 50 ml. of benzene was charged. Subsequently, 31.2 ml. (300millimoles) of cyclohexanol were added thereto and refluxing waseffected at a temperature of 90 to 100 C for about 2 hours.

The ethanol produced was removed together with benzene from the reactionmixture by azeotropic distillation, and further unreacted materials wereremoved by distillation under reduced pressure.

There were obtained 25.5 g. of vanadyl tricyclohexoxide as the reactionproduct. The same was a yellow crystalline solid having a melting pointof 44.5 C.

One liter of normal heptane was charged into a 2 l. flask. A mixed gasof 40 mole percent of ethylene and 60 mole percent of propylene waspassed to the resultant flask placed in a thermostat maintained at 30 C.at the rate of NL/min. until the heptane was saturated. Subsequently, 3millimoles of ethyl aluminum sesquichloride (A1Et, C1, and 0.3 millimoleof vanadyl tricyclohexoxide were added in that order, and furtherethylene and propylene were passed in for 30 minutes while stirring.

3O milliliters of methanol were added to the reaction mixture to stopthe reaction. After washing the resultant reaction mixture sufficientlywith methanol, the mixture was charged into a large amount of methanolto coagulate the copolymer. After drying the coagulum, there wereobtained 28.4 g. of a white amorphous solid copolymer.

The intrinsic viscosity of the copolymer in a xylene solution measuredat 70 C. was 2.4 d1./g. The propylene content of the copolymer asdetermined by infrared absorption spectrum was 40.8 mole percent.

Using vanadyl trichloride in place of vanadyl tricyclohexoxide givesonly 23.5 g. of the copolymer, which shows that vanadyl tricyclohexoxidegives a higher polymerization activity.

In carrying out the polymerization under the same conditions asmentioned above except for the use of butene-l in place of propylene,there were obtained 16.3 g. of copolymer.

EXAMPLE 2 A ml. four-necked flask provided with a stirrer, thermometer,reflux condenser and dropping funnel was evacuated and filled withargon, and 14.3 g. 39.3 millimoles) of vanadyl tricyclohexoxidedissolved in 25 ml. of benzene was charged. Then, 2.79 ml. (39.3millimoles) of acetyl chloride dissolved in 10 ml. of benzene weregradually added dropwise while stirring. After completion of thedropwise addition, refluxing was effected at an external temperature of100 C. for about 1 hour.

Removing the solvent and cyclohexyl acetate from the reaction mixture bydistillation, there were obtained 12 g. ofmonochlorovanadyl-dicyclohexoxide.

Repeating the reaction in the same manner as in Example 1 except that0.3 millimole of monochlorovanadyl-dicyclohexoxide thus obtained wasused in place of vanadyl tricyclohexoxide there were obtained 30.4 g. ofan amorphous solid copolymer having an intrinsic viscosity of 4.30d1./g. and a propylene content of 40.2 mole percent.

EXAMPLE 3 By mixing and reacting a solution of 4.62 g. (30 millimoles)of bomeol in 50 ml. of benzene and a solution of 5.20 g. (30 millimoles)of vanadyl trichloride in 50 ml. of benzene, there was prepared asolution of dichlorovanadylbomyloxide having a concentration of 0.3millimole/l.

Repeating the polymerization in the same manner as in Example 1 exceptthat 0.3 millimole of dichlorovanadylbornyloxide thus produced in placeof vanadyltricyclohexoxide, 3 millimoles of trihexyl aluminum in placeof ethyl aluminum sesquichloride and l l. of tetrachloroethylene as asolvent in place of normal heptane were used, there were obtained 8.74g. of a white amorphous copolymer having an intrinsic viscosity of 3.21dl./g. and a propylene content of 50.7 mole percent.

EXAMPLE 4 1 liter of normal heptane was charged into a 2 l. flask. Amixed gas of 40 mole percent of ethylene and 60 mole percent ofpropylene was passed thereto at 15 C. to saturate the normal heptane.millimoles of 1,4-hexadiene, 6 millimoles of ethyl aluminumsesquichloride and 0.6 millimole of monochlorovanadyl-dicyclohexoxidewere added thereto, and the reaction was efi'ected for 50 minutes whilepassing in the mixed gas at the afore-described rate with stirring.

Treating the reaction mixture obtained in the same manner as in Example1, there were obtained 23.2 g. of a white solid copolymer having anintrinsic viscosity of 0.91 dl./g., a propylene content of 28.7 molepercent and an iodine value of 17.6.

Repeating the above reaction with vanadyl trichloride in place ofmonochlorovanadyl-dicyclohexoxide, there were obtained 17.7 g. of awhite solid copolymer having an intrinsic viscosity of 1.58 d1./g., apropylene content of 35.3 mole percent and an iodine value of 10.6.

As is obvious from these experiments, monochlorovanadyldicyclohexoxideinvolves less retarding effect and increases the copolymerizability ofthe diene.

EXAMPLE 5 Repeating the reaction in the same manner as in Example 4except that 80 millimoles of isoprene in place of 1,4-hexadiene, 3millimoles of ethyl aluminum sesquichloride and 0.3 millimole ofmonochlorovanadyl-dicyclohexoxide were used, there were obtained 16.1 g.of a white solid copolymer having an intrinsic viscosity of 0.85 d1./g.,a propylene content of 2 1.5 mole percent and an iodine value of 3.6.

Repeating the foregoing reaction with the use of vanadyl trichloride inplace of monochlorovanadyl-dicyclohexoxide, there were obtained 7.83 g.of copolymer having an intrinsic viscosity of 1.32 dl./g., a propylenecontent of 35.3 mole percent and an iodine value of 0.9.

As is obvious from these experiments, monochlorovanadyldicyclohexoxideinvolves less retarding effect and increases the copolymerizability ofthe diene.

EXAMPLE 6 Repeating the reaction in the same manner as in Example exceptthat ethylaluminium dichloride was used in place of ethylaluminiumsesquichloride, there were obtained 3.42 g. of a copolymer having anintrinsic viscosity of 0.70 dl./g., a propylene content of 35.7 molepercent and an iodine value of 18.6.

The iodine value of a copolymer obtained by repeating the foregoingreaction with vanadyl trichloride in place ofmonochlorovanadyl-dicyclohexoxide was 7.6.

EXAMPLE 7 Mixing and reacting a solution of 2.98 g. (24 millimoles) of5-hydroxymethyl-2-norbornene in 20 ml. of benzene and a solution of 2.08g. (12 millimoles) of vanadyl chloride in 20 ml. of benzene, there wasprepared a solution of monochlorovanadyl-dinorbornylmethoxide having aconcentration of 0.3 millimole/ml. Repeating the polymerization in thesame manner as in Example 5 except thatmonochlorovanadyl-dinorbornylmethoxide was used in place ofmonochlorovanadyl-dicyclohexoxide, there were obtained 2.60 g. of awhite solid copolymer having an intrinsic viscosity of 0.80 dl./g., apropylene content of 32.3 mole percent and an iodine value of 12.6.

EXAMPLE 8 1 liter of normal heptane was charged into a 2 l. flask. Amixed gas of 40 mole percent of ethylene and 60 mole percent ofpropylene and hydrogen were passed at 30 C to the resultant normalheptane at the rates of Nl./min. and 2 N1./min. respectively to saturatethe normal heptane. 10 millimoles of 5-ethylidene-2-norbornene, 4millimoles of ethylaluminum sesquichloride and 0.2 millimole ofvanadyltricyclohexoxide were added, and the reaction was effected for 30minutes while passing in the mixed gas and hydrogen at the foregoingrates with stirring.

Treating the reaction mixture in the same manner as in Example 1, therewere obtained 15.8 g. of a white solid copolymer having an intrinsicviscosity of 1.50 dl./g., a propylene content of 36.3 mole percent andan iodine value of 19.5.

We claim:

1. A method for preparing an olefinic hydrocarbon copolymer whichcomprises contacting ethylene and an alphaolefin having 3 to carbonatoms, with or without a polyene compound, with (A) a vanadium compoundhaving the general formula VO(OR),,,X;, in which R is a radicalcontaining cycloaliphatic hydrocarbon having 5 to 20 carbon atoms, X isa halogen atom and m is an integer from 1 to 3, and (B) anorganoaluminum compound having the general formula AlR',,X' in which Ris a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogenatom and n is a number from 1 to 3, the concentration of (A) in thereaction medium being from 10" millimoles per liter to 50 millimoles perliter, and the molar ratio of (B) to (A) being from 1:1 to l0,000:l.

2. A method as in claim 1 in which a polyene is present, said polyenebeing a non-conjugated diene.

3. A method as in claim 1 in which a polyene is present, said polyenebeing a conjugated diene.

4. A method as in claim 1 in which the said cyclic hydrocarbon radicalis cyclohexyl.

5. A method as in claim 4 in which the vanadium compound is vanadyl tricclohexoxide.

6. A meth as in claim 4 in which the vanadium compound ismonochlorovanadyl-dicyclohexoxide.

7. A method as in claim 1 in which said cyclic hydrocarbon radical isbomyl.

8. A method as in claim 7 in which the vanadium compound isdichlorovanadylbomyloxide.

9. A method as in claim 1 in which said cyclic hydrocarbon radical isnorbomyl.

10. A method as in claim 9 in which the vanadium compound ismonochlorovanadyl-dinorbomyloxide.

11. A method as in claim 1 in which (B) is an alkyl aluminum halide.

12. A method as in claim 11 in which the alkyl aluminum halide is analkyl aluminum sesquihalide.

13. A method as in claim 11 in which the alkyl aluminum halide is analkyl aluminum dihalide.

14. A method as in claim 1 in which (B) is a trialkyl aluminum.

15. A method for preparing an olefinic hydrocarbon copolymer whichcomprises contacting ethylene and an alphaolefin having 3 to 20 carbonatoms, with or without a polyene compound, with (A) a vanadium compoundhaving the general formula VO(OR),,,X in which R is a cyclic hydrocarbonradical selected from the group consisting of cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, 3-cyclopentenyl, 2-cyclohexenyl,2-cycloheptenyl, 4-cyclooctenyl, 2- methyl-cyclopentenyl,3-tertiary-butyl-cyclohexyl, 4-pheny1- cyclohexyl,1,3-dimethyl-cyclohexyl, 3-methyl-6-isopropylcyclohexyl,cyclopentyl-methyl, cyclohexyl-ethyl, cycloheptyl-ethyl,2,2-biscyclo-hexyl-ethyl, 2-norbomyl, bomyl, 5-norbomen-Z-yl, 3-pinanyl,cyclopentane-spiro-cyclobutan-3-yl, spiro-bicyclohexan-4-yl, 2-indenyl,and l-indanyl, X is a halogen atom and m is an integer from 1 to 3, and(B) an organo-aluminum compound having the general formula AlR,,X';, inwhich R is a hydrocarbon radical having 1 to 20 carbon atoms, X is ahalogen atom, and n is a number from 1 to 3, the concentration of (A) inthe reaction medium being from 0.1 to 10 millimoles per liter and themolar ratio of (B) to (A) being from 2:1 to 300:1.

16. A method as in claim 15 in which a polyene is present, said polyenebeing a non-conjugated diene.

17. A method as in claim 15 in which a polyene is present, said polyenebeing a conjugated diene.

18. A method as in claim 3 in which the said cyclic hydrocarbon radicalis cyclohexyl.

19. A method as in claim 18 in which the vanadium compound is vanadyltricyclohexoxide.

20. A method as in claim 18 in which the vanadium compound ismonochlorovanadyl-dicyclohexoxide.

21. A method as in claim 3 in which said cyclic hydrocarbon radical isbomyl.

22. A method as in claim 21 in which the vanadium compound isdichlorovanadylbomyloxide.

23. A method as in claim 3 in which said cyclic hydrocarbon radical isnorbomyl.

24. A method as in claim 23 in which the vanadium compound ismonochlorovanadyl dinorbornyloxide.

25. A method as in claim 3 in which (B) is an alkyl aluminum halide.

26. A method as in claim 25 in which the alkyl aluminum halide is analkyl aluminum sesquihalide.

27. A method as in claim 25 in which the alkyl aluminum halide is analkyl aluminum dihalide.

28. A method as in claim 3 in which (B) is a trialkyl aluminum.

2. A method as in claim 1 in which a polyene is present, said polyenebeing a non-conjugated diene.
 3. A method as in claim 1 in which apolyene is present, said polyene being a conjugated diene.
 4. A methodas in claim 1 in which the said cyclic hydrocarbon radical iscyclohexyl.
 5. A method as in claim 4 in which the vanadium compound isvanadyl tricyclohexoxide.
 6. A method as in claim 4 in which thevanadium compound is monochlorovanadyl-dicyclohexoxide.
 7. A method asin claim 1 in which said cyclic hydrocarbon radical is bornyl.
 8. Amethod as in claim 7 in which the vanadium compound isdichlorovanadylbornyloxide.
 9. A method as in claim 1 in which saidcyclic hydrocarbon radical is norbornyl.
 10. A method as in claim 9 inwhich the vanadium compound is monochlorovanadyl-dinorbornyloxide.
 11. Amethod as in claim 1 in which (B) is an alkyl aluminum halide.
 12. Amethod as in claim 11 in which the alkyl aluminum halide is an alkylaluminum sesquihalide.
 13. A method as in claim 11 in which the alkylaluminum halide is an alkyl aluminum dihalide.
 14. A method as in claim1 in which (B) is a trialkyl aluminum.
 15. A method for preparing anolefinic hydrocarbon copolymer which comprises contacting ethylene andan alpha-olefin having 3 to 20 carbon atoms, with or without a polyenecompound, with (A) a vanadium compound having the general formulaVO(OR)mX3 m, in which R is a cyclic hydrocarbon radical selected fromthe group consisting of cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, 3-cyclopentenyl, 2-cyclohexenyl, 2-cycloheptenyl,4-cyclooctenyl, 2-methyl-cyclopentenyl, 3-tertiary-butyl-cyclohexyl,4-phenyl-cyclohexyl, 1,3-dimethyl-cyclohexyl,3-methyl-6-isopropyl-cyclohexyl, cyclopentyl-methyl, cyclohexyl-ethyl,cycloheptyl-ethyl, 2,2-biscyclo-hexyl-ethyl, 2-norbornyl, bornyl,5-norbornen-2-yl, 3-pinanyl, cyclopentane-spiro-cyclobutan-3-yl,spiro-bicyclohexan-4-yl, 2-indenyl, and 1-indanyl, X is a halogen atomand m is an integer from 1 to 3, and (B) an organo-aluminum compoundhaving the general formula AlR''nX''3 n, in which R'' is a hydrocarbonradical having 1 to 20 carbon atoms, X'' is a halogen atom, and n is anumber from 1 to 3, the concentration of (A) in the reaction mediumbeing from 0.1 to 10 millimoles per liter and the molar ratio of (B) to(A) being from 2:1 to 300:1.
 16. A method as in claim 15 in which apolyene is present, said polyene being a non-conjugated diene.
 17. Amethod as in claim 15 in which a polyene is present, said polyene beinga conjugated diene.
 18. A method as in claim 3 in which the said cyclichydrocarbon radical is cyclohexyl.
 19. A method as in claim 18 in whichthe vanadium compound is vanadyl tricyclohexoxide.
 20. A method as inclaim 18 in which the vanadium compound ismonochlorovanadyl-dicyclohexoxide.
 21. A method as in claim 3 in whichsaid cyclic hydrocarbon radical is bornyl.
 22. A method as in claim 21in which the vanadium compound is dichlorovanadylbornyloxide.
 23. Amethod as in claim 3 in which said cyclic hydrocarbon radical isnorbornyl.
 24. A method as in claim 23 in which the vanadium compound ismonochlorovanadyl dinorbornyloxide.
 25. A method as in claim 3 in which(B) is an alkyl aluminum halide.
 26. A method as in claim 25 in whichthe alkyl aluminum halide is an alkyl aluminum sesquihalide.
 27. Amethod as in claim 25 in which the alkyl aluminum halide is an alkylaluminum dihalide.
 28. A method as in claim 3 in which (B) is a trialkylaluminum.